Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
  • C07C407/003—Separation; Purification; Stabilisation; Use of additives
  • C07C407/006—Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• This invention relates to peroxygen compounds and especially to ketone peroxide containing compositions.
• ketone peroxides A major commercial use of ketone peroxides is in the cross-linking of resins and particularly unsaturated polyester resins either alone or, more commonly, in conjunction with a metal containing catalyst such as cobalt naphthenate, and possibly, organic co-accelerators.
• the ketone peroxide is usually used in solution in an inert solvent.
• the present invention provides a composition comprising one or more ketone peroxides, one or more inert solvents therefor, and stabilising quantity of one or more amine compounds, said amine compounds wholly consisting of one or more aliphatic or heterocyclic amines.
• Each amine/ peroxide combination according to the invention shows a dilferent degree of improvement in comparison with the untreated peroxide solution and so in some instances a greater quantity of amine may be necessary to achieve a desired effect.
• many amines when present in excessive quantity in a ketone peroxide solution, for example in to 15% by weight of the composition, cause instability but the concentration threshold where the stability effect of each amine, on each peroxide solution, starts to diminish is different in each instance. It is necessary therefore to determine by test in each instance whether a stabilising quantity of amine is present in a ketone peroxide solution.
• hydrophilic solvents which are advantageously used are glycols, for example one or more of mono-, di-, tri-, or tetra ethylene glycol, propylene glycol, dipropylene glycol, pentylene glycol or hexylene glycol, glycol ethers, such as ethylene glycol monoethyl ether and its methyl and butyl derivatives (Cellosolvej methyl Cellosolve and butyl Cellosolve), phosphate esters, such as trialkyl phosphates for example triethyl phosphate, and low molecular weight aliphatic alcohols.
• Suitable hydrophobic solvents are the phthalate esters such as dimethyl phthalate or di-butyl phthalate.
• ketone peroxides may have been prepared in a single stage reaction in a suitable solvent.
• a reaction mixture comprising the corresponding ketone, hydrogen peroxide, for example in from 60% to w./w. concentration, and a catalyst, for example, a suitable source of hydrogen ion, may be suspended in a suitable inert solvent, for example a low molecular weight trialkyl phosphate, or a phthalate ester, or a glycol, and allowed to react at for example, temperatures of from 0 C. to 60 C.
• a concentrated ketone peroxide solution may be diluted with a suitable inert solvent to the concentration required for a particular end use, either before or after the introduction of amines according to this invention.
• Ketone peroxide solutions to which such (so-accelerators have been added are very unstable with respect to activity. After only short periods of storage gel times become extremely long.
• the ketone peroxide solution was an amine-containing composition according to this invention it was found that there was little decrease in activity on storage and that, in use in cross-linking, the composition possessed the expected advantages accruing from the presence of co-accelerators, namely, an improvement in the relationship between time to exotherm maximum and gel time.
• compositions are amine containing solutions in inert solvents of methyl ethyl ketone peroxide, diacetone alcohol peroxide, methyl isobutyl ketone peroxide or cyclohexanone peroxide also containing acetyl acetone or actoacetic ester co-accelerators.
• the amine stabiliser is tri-isopropanolamine.
• the co-accelerator is present in from 0.1 to 10% by weight preferably from 0.5 to 10% by weight of the composition.
• compositions provided by this invention besides their activity constancy tend to have improved properties in respect of flammability and readiness to explode when subjected to shock or friction.
• the compositions can also contain other known peroxide stabilisers, for example 2,6 dipicolinic acid or ethylene diamine tetraacetic acid.
• Other additives such as wetting agents can also be added if desired.
• the present invention also provides processes for crosslinking unsaturated polyester resins using ketone peroxide containing compositions herein and also for polymerised resin masses produced by such a process.
• Sample I without amine
• Sample II 20 m.e./l. of triisopropanolamine and 300 p.p.m. of 2,6-dipicolinic acid added.
• the activity and the active oxygen content were measured immediately after the preparation and after 3 and 6 months storage at room temperature.
• Sample I without amine
• Sample H m.e./l. of tri-isopropanolamine and 200 p.p.m. of 2,6-dipicolinic acid added.
• the activity and the active oxygen content were measured immediately after the preparation and after 14 days warm storage at C.
• Sample III m.e./l. of triethylamine and 1000 ppm.
• Sample III 25 m.e./l. of tri-isopropanolamine and 100 p.p.m. of 2,6-dipicolinic acid added.
• the activity and the active oxygen content were measured immediately after the preparation and after 14 days warm storage at 50 C.
• Solution I contained 10% water
• II contained 0.8 g./ kg. tri-isopropanolamine
• III contained 10% of a 4% aqueous tri-isopropanolamine solution.
• the activity was 8 measured at 20 C. with 10% peroxide solution and 2% of cobalt and accelerator.
• Part I was used unchanged and 0.2% of 2,4,6 trimethyl pyridine was added to Part 11.
• a composition as claimed in claim 1 wherein said heterocyclic ring compound is a member of the group consisting of pyridine, piperidine, a picoline, a lutidine, a collidine, an imidazole, and a triazole.
• ketone peroxide is a peroxide of a member of the group consisting of acetone, methyl ethyl ketone, methyl iso butyl ketone, methyl isoamyl ketone, ethyl amyl ketone, diisobutyl ketone, cyclohexanone, alkyl cyclohexanone, acetophenone, diacetyl ketone, acetyl acetone, and diacetone.
• composition as claimed in claim 1 containing, in addition, a compound selected from the group consisting of acetyl acetone and lower alkyl acetoacetates as coaccelerator.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polyesters Or Polycarbonates (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Dental Preparations (AREA)
• Detergent Compositions (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=25973459

Family Applications (1)

Country Status (11)

Cited By (6)

Families Citing this family (4)

Family Cites Families (2)

• 1966
  • 1966-09-23 DE DEE32532A patent/DE1289047B/de active Pending
• 1967
  • 1967-05-31 DE DE1618322A patent/DE1618322C3/de not_active Expired
  • 1967-09-06 NO NO00169641A patent/NO128439B/no unknown
  • 1967-09-12 SE SE12571/67A patent/SE345847B/xx unknown
  • 1967-09-22 GB GB43228/67A patent/GB1199744A/en not_active Expired
  • 1967-09-22 DK DK474867AA patent/DK120846B/da unknown
  • 1967-09-22 NL NL676713010A patent/NL139960B/xx not_active IP Right Cessation
  • 1967-09-22 AT AT866267A patent/AT275490B/de active
  • 1967-09-22 CH CH1327367A patent/CH491075A/de not_active IP Right Cessation
  • 1967-09-22 FR FR1551955D patent/FR1551955A/fr not_active Expired
  • 1967-09-25 US US670444A patent/US3645908A/en not_active Expired - Lifetime
• 1968
  • 1968-10-22 ES ES345363A patent/ES345363A1/es not_active Expired
• 1973
  • 1973-06-04 NL NL7307731.A patent/NL158799C/xx not_active IP Right Cessation

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